Brominated flame retardants and polychlorinated biphenyls in fish from the river Scheldt, Belgium

Levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and polychlorinated biphenyls (PCBs) were measured in several fish species originating from the river Scheldt (Belgium). Five sampling locations were chosen in a highly industrialized area along the river, while two ponds in the vicinity of the river served as reference sites. The present study is a follow-up of a survey performed in 2000 which reported extremely high levels of PBDEs and HBCDs in eel (Anguilla anguilla) collected from the same region (Oudenaarde, Flanders). The sum of tri- to hepta-BDE congeners (2270+/-2260 ng/g lipid weight (lw), range 660-11500 ng/g lw) and total HBCDs (4500+/-3000 ng/g lw, range 390-12100 ng/g lw) were one order of magnitude higher than levels usually reported from freshwater systems, indicating the presence of point sources. In most samples, levels of total HBCDs were higher than those of PBDEs, probably due to the high density of factories using HBCD as an additive brominated flame retardant (BFR). The high values of HBCDs were confirmed by both gas- and liquid-chromatography-mass spectrometry. Although BFR levels were between the highest ever reported in freshwater ecosystems, PCBs could be detected at even higher concentrations (16000+/-14300 ng/g lw, range 3900-66600 ng/g lw), being among the highest levels recorded in Belgium. The inter-sampling site variation of PBDEs, HBCDs and PCBs was comparable. All locations presented similar PBDE congener profiles, with BDE 47 being the dominant congener, followed by BDE 100, BDE 99 and BDE 49, probably originating from the former use of the penta-BDE technical mixture. In order to estimate the impact of these point sources on human exposure, we further focussed on eels which showed a considerable decrease in the PBDE and HBCD levels between 2000 and 2006. Due to the wide span in concentrations between the different sampling locations, a variable contribution to the total human exposure through local eel consumption was estimated. The calculated daily intake ranged from 3 ng to 330 ng PBDEs/day for normal eel consumers, but was as high as 9800 ng PBDEs/day for anglers, which may be considered at risk.     

Brominated flame retardants and polychlorinated biphenyls in human breast milk from several locations in India: potential contaminant sources in a municipal dumping site

This study investigated the status of contamination of organohalogen compounds (OCs) such as polychlorinated biphenyls (PCBs) and brominated flame retardant (BFRs), including polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in human milk samples from several locations in India. The levels of OCs were significantly higher in the milk of mothers living in and near municipal dumping site than other locations indicating that the open dumping sites for municipal wastes act as potential sources of these contaminants in India. The PCB concentrations observed in this study tended to decrease compared to those in the matched locations reported previously, probably due to the restriction of technical PCB usage in India. PBDE levels in human milk were two to three folds lower than those of PCBs in all the sampling locations investigated. Congener profiles of PCBs and PBDEs were different between samples from the dumping site mothers and general populations in other areas suggesting the presence of region-specific sources and pathways. HBCDs were detected in human milk from only two sites, with much lower concentrations and detection frequencies compared to PCBs and PBDEs. When hazard quotients (HQs) of PCBs and PBDEs were estimated for infant health risk, the HQs in some milk samples from the dumping site exceeded the threshold value (HQ > 1) of PCBs, indicating the potential risk for infants in the specific site.     

Tetrabromobisphenol-A, hexabromocyclododecane and its degradation products in UK human milk: relationship to external exposure

Tetrabromobisphenol-A (TBBP-A), hexabromocyclododecane (HBCD) and its degradation products were determined in 34 human milk samples from Birmingham, UK. TBBP-A was detected in 36% of samples (average=0.06 ng g(-1) lw), with HBCDs detected in all samples (average ΣHBCDs=5.95 ng g(-1) lw). α-HBCD comprised 62-95% ΣHBCDs while β- and γ-HBCD constituted 2-18% and 3-33% respectively. Enantioselective enrichment of (-)-α-HBCD (average enantiomer fraction=0.29) was observed indicating potential enantioselectivity associated with HBCD absorption, metabolism and/or excretion. The degradation products pentabromocyclododecenes (average=0.04 ng g(-1) lw; n=9) and tetrabromocyclododecadienes (average=0.15 ng g(-1) lw; n=25) were detected for the first time in human tissues. Average exposures of a nursing infant to ΣHBCDs and TBBP-A (35 and 1 ng kg(-1) bw day(-1) respectively) via breast milk exceeded upper-bound dietary intakes of both UK adults and toddlers. Using a simple pharmacokinetic model, intakes of UK adults via inhalation, diet and dust ingestion were converted to predicted body burdens. Predictions compared well with those observed for HBCDs but observed body burdens of TBBP-A exceeded predictions. This may indicate the human half-life of TBBP-A is greater than observed previously, that intakes may be underestimated, or that concentrations reported here reflect recent elevated episodic exposure.     

Environmental impact and human exposure to PCBs in Guiyu, an electronic waste recycling site in China

PCB levels in fish (collected from local rivers), atmosphere and human milk samples have been studied to determine the exposure levels of PCBs for local residents and e-waste workers in Guiyu, a major electronic waste scrapping center in China. The source appointment and correlation analyses showed that homologue composition of PCBs in 7 species of fish were consistent and similar to commercial PCBs Aroclor 1248. PCB levels in air surrounding the open burning site were significantly higher than those in residential area. Inhalation exposure contributed 27% and 93% to the total body loadings (the sum of dietary and inhalation exposure) of the local residents, and e-waste workers engaged in open burning respectively. Total PCB concentrations in human milk ranged from N.D. to 57.6 ng/g lipid, with an average of 9.50 ng/g lipid. The present results indicated that commercial PCBs derived from e-waste recycling are major sources of PCBs accumulating in different environmental media, leading to the accumulation of high chlorinated biphenyls in human beings.     

Halogenated flame retardants in home-produced eggs from an electronic waste recycling region in South China: Levels,composition profiles,and human dietary exposure assessment

Three regulated halogenated flame retardants (HFRs), i.e., polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and hexabromocyclododecanes (HBCDs), and several alternative HFRs (AHFRs) including Dechlorane Plus (DP), decabromodiphenyl ethane (DBDPE), and 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), were investigated in the home-produced eggs from three recycling sites and a reference site in an electronic waste (e-waste) recycling region, South China. Mean levels of HFRs in eggs from the recycling sites ranged 2640–14 100, 700–1620, 44–350, and 720–3920 ng/g lipid weight for ∑PBDEs, ∑PBBs, ∑HBCDs, and ∑AHFRs, respectively, which were one to two orders of magnitude higher than those examined in the reference site. PBDEs were the predominant HFR in those eggs, with contributions > 50% to the total HFRs; followed by PBBs and the AHFRs (contributing 14–22% in average). The α-HBCD was the predominant diastereoisomers of HBCDs, with preferential enrichment of the (−)-enantiomer in most of the eggs; but no significant stereoselective enrichment of the DP isomers was observed in these eggs. The average estimated daily intakes (EDIs) of PBDEs, PBBs, HBCDs, and the AHFRs via eggs from the recycling sites ranged 4200–20 000, 1120–2440, 80–490, and 970–4530 ng/day, respectively, which were one to two orders of magnitude higher than those reported from other parts of the world. The potential adverse effects of these HFRs to human health in the e-waste sites should be further investigated. This is the first report on the isomer compositions of DP and the chiral signatures of HBCDs in hen eggs.     

Bioaccumulation of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in wild aquatic species from an electronic waste (e-waste) recycling site in South China

Water and several wild aquatic species including Chinese mysterysnail, prawn, fish, and water snake were collected from a reservoir surrounded by several e-waste recycling workshops in South China. The samples were examined to investigate the levels and bioaccumulation extent of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) released from electronic waste (e-waste) which was processed by crude recycling method. Elevated levels of PBDEs [52.7 to 1702 ng/g wet weight (ww)] and PCBs (20.2-25958 ng/g ww) were found in the collected biota species compared to that in the reference samples (13.0-20.5 ng/g ww for PBDEs and 75.4-82.8 ng/g ww for PCBs). log BAF (bioaccumulation factor) ranged from 2.9 to 5.3 for PBDEs and from 1.2 to 8.4 for PCBs, depending on congeners and species. The relationship between log BAFs and log K(OW) (octanol-water partition coefficient) can be adequately described by species-specific parabolic models wherein log BAFs generally increased at log K(OW)<7 then decreased with further increasing log K(OW) both for PBDEs and PCBs. The exceptions were for Chinese mysterysnail and prawn, in which the log BAFs showed a positive linear correlation with log K(OW) for PBDEs. Some PBDE and PCB congeners showed BAF values declining from the general trend predicted by K(OW), largely attributing to metabolism of these congeners in species sampled.     

Flame retardants and organochlorines in indoor dust from several e-waste recycling sites in South China: Composition variations and implications for human exposure

Several classes of flame retardants, such as polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), dechlorane plus (DPs), and organophosphate flame retardants (PFRs), together with polychlorinated biphenyls (PCBs) were measured in indoor dust from five villages located in three e-waste recycling regions in Guangdong Province, South China. The medians of PBDEs, NBFRs, and PFRs in dust in five sites ranged from 685–67,500, 1460–50,010, and 2180–29,000 ng/g, respectively. These concentrations were much higher than the medians of PCBs (52–2900 ng/g). BDE 209 and decabromodiphenyl ethane (DBDPE) were the two major halogen flame retardants in dust, while tris-(1-chloro-2-propyl) phosphate (TCIPP) and triphenyl phosphate (TPHP) were the major PFRs. Principle component analysis revealed the different pollutant patterns among different sites. The estimated median human exposures of PBDEs, NBFRs, PFRs, and PCBs via dust ingestion were 1.1–24.1, 0.73–20.3, 1.36–23.5, and 0.04–0.93 ng/kg bw/day for adults, and 16.2–352, 10.7–296, 19.9–343, 0.05–0.61, 0.65–13.6 ng/kg bw/day for toddlers, respectively. Residents from Site 5 had the highest exposure (95 percentile levels and high dust ingestion for toddlers) of PBDEs (3920 ng/kg bw/day), NBFRs (3200 ng/kg bw/day), and PFRs (5280 ng/kg bw/day). More attention should be paid to the contamination with NBFRs and PFRs, instead of PCBs, in these e-waste recycling regions, and local public health threat from PBDE alternatives should remain of concern. To the best of our knowledge, this is the first study on human exposure assessment of PFRs at e-waste sites.     

Novel brominated flame retardants in food composites and human milk from the Chinese Total Diet Study in 2011: Concentrations and a dietary exposure assessment

On the basis of the fifth Chinese total diet study (TDS) performed in 2011, the dietary exposure of the Chinese population to novel brominated flame retardants (NBFRs) was assessed. Six NBFRs were determined in 80 composite samples from four animal origin food groups and 29 pooled human milk samples. Based on gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS) analysis, the levels of the total NBFRs ranged from < LOD to 70.2 ng/g lipid weight (lw) in food composites and from 2.48 to 23.9 ng/g lw in human milk samples. Decabromodiphenyl ethane (DBDPE), with mean levels of 9.03 ng/g lw in food composites and 8.06 ng/g lw in human milk, was the most abundant compound in the total NBFRs. No obvious spatial distribution patterns in China were observed in food samples or human milk. The average estimated daily intake (EDI) of total NBFRs via food consumption for a “standard Chinese man” was 4.77 ng/kg bodyweight (bw)/day, with a range of 0.681 to 18.9 ng/kg bw/day. Meat and meat products were the main dietary source of NBFRs, although levels of NBFRs in aquatic food were found to be the highest among the four food groups. The average EDI of total NBFRs for nursing infants was 38.4 ng/kg bw/day, with a range of 17.4 to 113 ng/kg bw/day, which was approximately eight-fold higher than the EDI for adults, suggesting the heavy body burden of NBFRs on nursing infants. The levels and EDI of DBDPE in the present study were similar to or higher than those of legacy BFRs (i.e., PBDEs and HBCD) in the TDS 2007, indicating that DBDPE, as a main alternative to PBDEs, might have become the primary BFR used in China.     

Country specific comparison for profile of chlorinated,brominated and phosphate organic contaminants in indoor dust. Case study for Eastern Romania, 2010

We have evaluated the levels and specific profiles of several organohalogenated contaminants, including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and flame retardants (FRs), such as polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), novel brominated FRs (NBFRs), and organophosphate FRs (OPFRs), in 47 indoor dust samples collected in 2010 from urban locations from Iasi, Eastern Romania. The dominant contaminants found in the samples were OPFRs (median sum OPFRs 7890 ng/g). Surprisingly, OCPs were also measured at high levels (median 1300 ng/g). Except for BDE 209 (median 275 ng/g), PBDEs were present in dust samples at relatively low levels (median sum PBDEs 8 ng/g). PCBs were also measured at low levels (median sum PCBs 35 ng/g), while NBFRs were only occasionally detected, showing a low usage in goods present on the Romanian market. The results of the present study evidence the existence of a multitude of chemical formulations in indoor dust. FRs are usually associated to human exposure via ingestion of dust, but other chemicals, such as OCPs, are not commonly reported in such matrix. Although OCPs were found at comparable levels with OPFRs in Romanian dust, OCPs possess a higher risk to human health due to their considerably lower reference dose (RfD) values. Indeed, the OCP exposure calculated for various intake scenarios was only 2-fold lower than the corresponding RfD. Therefore, the inclusion of OCPs as target chemicals in the indoor environment becomes important for countries where elevated levels in other environmental compartments have been previously shown.     

Concentrations of PCDD/Fs,PCBs and PBDEs in breast milk of women from Catalonia,Spain: A follow-up study

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were determined in breast milk from women living in the vicinity of a new hazardous waste incinerator (HWI) in Catalonia, Spain. The results were compared with the levels obtained in two previous surveys carried out in 1998 (baseline study) and 2002. The current concentrations of PCDD/Fs in breast milk ranged from 45 to 143 pg/g fat (2.8 to 11.2 pg WHO-TEQ/g fat), while total PCBs ranged from 114 to 617 pg/g fat (2.8 to 17.6 pg WHO-TEQ/g fat). PBDE concentrations (sum 15 congeners) ranged from 0.57 ng/g fat to 5.9 ng/g fat, with a mean value of 2.5 ng/g fat. A general decrease of the concentrations for PCDD/Fs and both planar and total PCBs was observed. Regarding to PBDE concentrations in breast milk, similar levels between the 2002 and the present study were noted. The levels of PCDD/Fs and PCBs in milk of women living in urban areas were higher than those corresponding to the industrial zones (38% and 40%, respectively). However, the current PBDE levels were slightly lower (13%) in the urban than in the industrial zone. For PCDD/Fs and PCBs, the current decreases are in accordance with the reduction in the dietary intake of these pollutants found in recent studies carried out in the same area of study.     

Analysis of human milk to assess exposure to PAHs,PCBs and organochlorine pesticides in the vicinity Mediterranean city Mersin,Turkey

Assessment of human exposure to environmental persistent organic pollutants such as organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) based on the levels in human breast milk provides a reasonable tool not only to assess the contaminant burden in mothers but also to assess potential exposure of breast-fed neonates. There are limited data on levels of PCBs and OCPs in humans but no previous reports from Turkey on chemically determined levels PAHs in human milk. The aim of this study was to report the levels and accumulation profiles of OCPs, PCBs and PAHs in 47 breast milk samples obtained from a Mediterranean city, Mersin. High resolution analyses were performed by a gas chromatography coupled with mass spectrometer (GC–MS). Dichlorodiphenyldichloroethane (4.4′-DDE) was the dominant pollutant. Beta-hexachlorocyclohexane (ß-HCH), dichlorodiphenyltrichloroethane (4.4′-DDT), dieldrin, hexachlorobenzene, oxy-chlordane, cis-heptachlorepoxide were the other main OCPs detected. Mean levels of ΣPCB congeners and WHO_PCB-TEQ were 9.94 and 0.001 ng/g lipid, respectively. PCB 153 showed the highest concentration (3.37 ng/g lipid), followed by PCB 138 and 180. For the dioxin-like PCBs, PCB 118 was the dominant (0.97 ng/g lipid). Naphthalene, phenanthrene, pyrene and fluoranthene were the major PAHs among the 16 PAHs detected. The estimated daily intakes of DDTs, PCBs, HCHs and HCB were not exceeded the tolerable daily intake (TDI) proposed by the Health Canada Guideline. These results indicate that the neonates of Mersin city are exposed to persistent organic pollutants analyzed in this study. However, neonates born in Mersin province are less exposed than the ones born in other regions, considering OCP and PCB levels in breast milk.     

Brominated flame retardants and organochlorines in the European environment using great tit eggs as a biomonitoring tool

Large-scale studies are essential to assess the emission patterns and spatial distribution of organohalogenated pollutants (OHPs) in the environment. Bird eggs have several advantages compared to other environmental media which have previously been used to map the distribution of OHPs. In this study, large-scale geographical variation in the occurrence of OHPs, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), was investigated throughout Europe using eggs of a terrestrial residential passerine species, the great tit (Parus major). Great tit eggs from 22 sampling sites, involving urban, rural and remote areas, in 14 European countries were collected and analysed (5-8 eggs per sampling site). The environmentally most important congeners/compounds of the analysed pollutants were detectable in all sampling locations. For PCBs, PBDEs and OCPs, no clear geographical contamination pattern was found. Sum PCB levels ranged from 143 ng/g lipid weight (lw) to 3660 ng/g lw. As expected, PCB concentrations were significantly higher in the sampled urban compared to the remote locations. However, the urban locations did not show significantly higher concentrations compared to the rural locations. Sum PBDEs ranged from 4.0 ng/g lw to 136 ng/g lw. PBDEs were significantly higher in the urbanized sampling locations compared to the other locations. The significant, positive correlation between PCB and PBDE concentrations suggests similar spatial exposure and/or mechanisms of accumulation. Significantly higher levels of OCPs (sum OCPs ranging from 191 ng/g lw to 7830 ng/g lw) were detected in rural sampling locations. Contamination profiles of PCBs, PBDEs and OCPs differed also among the sampling locations, which may be due to local usage and contamination sources. The higher variance among sampling locations for the PCBs and OCPs, suggests that local contamination sources are more important for the PCBs and OCPs compared to the PBDEs. To our knowledge, this is the first study in which bird eggs were used as a monitoring tool for OHPs on such a large geographical scale.     

Determinants of brominated flame retardants in breast milk from a large scale Norwegian study

Brominated flame retardants (BFRs), particularly polybrominated diphenyl ethers (PBDEs), are widely present in human populations. In order to investigate human exposure pathways and associations with socioeconomic and lifestyle factors, 393 breast milk samples from mothers living in various regions throughout Norway were analyzed. Up to ten PBDE congeners were measured in all the samples, hexabromocyclododecane (HBCD) and BDE-209 in subsets of 310 and 46, respectively. The median concentrations of the sum of the seven most prominent PBDEs (BDE-28, 47, 99, 100, 153, 154 and 183), BDE-209 and HBCD were 2.1, 0.32 and 0.86 ng/g lipids, respectively. These concentrations are comparable to the levels generally observed in human populations in Europe. The frequency distributions were quite skewed with long tails towards higher concentrations. Maternal age, parity, education, having a cohabitant employed as electrician, and ventilation were factors significantly associated with some of the BFRs, although these factors only explained a small amount of the variability (R² 0.04–0.16). The mothers' diet was not found to influence the breast milk PBDE and HBCD levels. Our results show that sources other than the diet are important for the variability seen in breast milk BFR concentrations and that exposure from the indoor atmosphere should be emphasized in future studies.     

Flame retardants in indoor dust and air of a hotel in Japan

Occurrence of flame retardants (FRs) in the indoor environment of highly flame-retarded public facilities is an important concern from the viewpoint of exposure because it is likely that FRs are used to a greater degree in these facilities than in homes. For this study, brominated flame-retardants (BFRs) and organophosphate flame-retardants and plasticizers (OPs), and brominated dibenzo-p-dioxins/furans (PBDD/DFs) were measured in eight floor dust samples taken from a Japanese commercial hotel that was assumed to have many flame-retardant materials. Concentrations of polybrominated diphenylethers (PBDEs) and hexabromocyclododecanes (HBCDs) varied by about two orders of magnitude, from 9.8–1700 ng/g (median of 1200 ng/g) and from 72–1300 ng/g (median of 740 ng/g), respectively. Concentrations of the two types of BFRs described above were most dominant among the investigated BFRs in the dust samples. It is inferred that BFR and PBDD/DF concentrations are on the same level as those in house and office dust samples reported based on past studies. Regarding concentrations of 11 OPs, 7 OPs were detected on the order of micrograms per gram, which are equivalent to or exceed the BFR concentrations such as PBDEs and HBCDs. Concentrations of the investigated compounds were not uniform among dust samples collected throughout the hotel: concentrations differed among floors, suggesting that localization of source products is associated with FR concentrations in dust. Passive air sampling was also conducted to monitor BFRs in the indoor air of hotel rooms: the performance of an air cleaner placed in the room was evaluated in terms of reducing airborne BFR concentrations. Monitoring results suggest that operation of an appropriate air cleaner can reduce both gaseous and particulate BFRs in indoor air.     

Polybrominated diphenyl ethers in the serum and breast milk of the resident population from production area, China

Polybrominated diphenyl ethers (PBDEs) have been produced in the south coast area of Laizhou Bay, Shandong Province in China, but little is known about the PBDE exposure level of residents to these compounds. We set out to assess potential health risks of PBDEs in the south coast area of the Laizhou Bay by determining the concentrations of PBDEs in serum and breast milk. We measured concentrations of eight PBDE congeners in serum and breast milk. The arithmetic means of Σ₈PBDE in pooled serum and breast milk were 613 ng/g lipid and 81.5 ng/g lipid, respectively. The highest concentration for Σ₈PBDE in all serum pools was 1830 ng/g lipid from the 41–50 year old female group. BDE-209 was the predominant congener, with the mean concentrations of 403 ng/g lipid in serum and 45.6 ng/g lipid in breast milk, respectively. BDE-209 averagely accounted for 65.8% and 54.2% of the total PBDEs, respectively. Our results suggest that high exposures to PBDEs have led to very high PBDE concentrations in serum and breast milk from the residents living in the south coast area of Laizhou Bay. High PBDE concentrations in human serum, particularly in women, pose a potential public health threat to local residents.     

The brominated flame retardants,PBDEs and HBCD,in Canadian human milk samples collected from 1992 to 2005; concentrations and trends

Human milk samples were collected from individuals residing in various regions across Canada mostly in the years 1992 to 2005. These included five large cities in southern Canada as well as samples from Nunavik in northern Quebec. Comparative samples were also collected from residents of Austin, Texas, USA in 2002 and 2004. More than 300 milk samples were analysed for the brominated flame retardants (BFRs), PBDEs and HBCD, by extraction, purification and quantification using either isotope dilution gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-MS. The Canadian total PBDE values in the years 2002–2005 show median levels of about 20 μg/kg on a lipid basis; a value significantly higher than in the 1980s and 1990s. Milk samples from Inuit donors in the northern region of Nunavik were slightly lower in PBDE concentrations than those from populated regions in the south of Quebec. Milk samples from Ontario contained slightly lower amounts of PBDEs in two time periods than those from Texas. HBCD levels in most milk samples were usually less than 1 ppb milk lipid and dominated by the α-isomer. This large data set of BFRs in Canadian human milk demonstrates an increase in the last few decades in human exposure to BFRs which now appears to have stabilized.     

Environmental release and behavior of brominated flame retardants

Recently, environmental problems relating to brominated flame retardants (BFRs) have become a matter of greater concern than ever before, because of the recent marked increase in levels of polybrominated diphenyl ethers (PBDEs) found in human milk in Sweden and North America. The question that arises is whether environmental levels of PBDEs and other BFRs will continue to increase, causing toxic effects to humans. In an attempt to elucidate the current state of the science of BFRs, we review the consumer demand for BFRs (mainly in Japan), the characteristics of waste flame-retarded products, sources of emission, environmental behavior, routes of exposure of humans, temporal trends, and thermal-breakdown products of BFRs. At present, flame-retarded consumer products manufactured 10-20 years ago, when PBDEs were frequently used, are being dumped. The possible major sources of emission of BFRs into the environment are effluent and flue gases from BFR factories and other facilities processing BFRs. With respect to the environmental behavior of BFRs, the lower brominated compounds are, on the whole, predicted to be more volatile, more water soluble, and more bioaccumulative than the higher brominated compounds. The most probable route for exposure of the general human population to PBDEs, especially the lower brominated congeners, is through the diet. The release of BFRs from consumer products treated with these compounds could also lead to human exposure. Temporal trends in PBDE levels in the environment and in humans worldwide seem to vary considerably, depending on the regions or country, with possible reflections of the historic and current use of PBDEs. The environment and the general human population are also exposed to the thermal-breakdown products of PBDEs, such as polybrominated and mixed brominated/chlorinated dibenzo-p-dioxins and dibenzofurans (PBDDs/DFs and mixed PXDDs/DFs).     

Maternal transfer of organochlorines and brominated flame retardants in blue tits (Cyanistes caeruleus)

Although eggs have frequently been used as a biomonitoring tool for contamination with organohalogenated pollutants (OHPs), few studies have investigated the processes of maternal transfer in birds. Here, maternal transfer of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) was investigated through comparison of the concentrations and profiles between whole homogenised female blue tits (Cyanistes caeruleus) and their eggs. In addition, we examined if there was an effect of laying order on the concentrations of PCBs, OCPs and PBDEs. PCBs were the most abundant contaminants in female blue tits and their eggs, followed by OCPs and PBDEs. Among the OCPs, p,p'-DDE was the most dominant compound and accounted for more than 80% of the sum OCPs. Egg concentrations decreased significantly in relation to the laying order from 1623+/-148 ng/g lipid weight (lw) to 1040+/-47 ng/g lw for the sum PCBs, from 342+/-24 ng/g lw to 235+/-17 ng/g lw for the sum OCPs and from 49+/-5 ng/g lw to 27+/-5 ng/g lw for the sum PBDEs. When reviewing all studies investigating laying order effects of OHPs in birds, no clear patterns emerged, which may be due to differences in study species and methodology among studies. Despite the fact that there were laying order effects in blue tit clutches, the variance in concentrations of PCBs and PBDEs was larger among clutches than within clutches. Variance in OCP concentrations among clutches was similar to the variance within clutches. These results suggest that one randomly collected blue tit egg from a clutch is useful as biomonitoring tool for PCBs and PBDEs, while for OCPs it is recommended to consistently use the same egg from the laying sequence as a biomonitoring tool. Lipid-normalized concentrations of sum PCBs, sum OCPs and sum PBDEs in female blue tits after clutch completion were comparable to the concentrations in the first-laid eggs. The egg/female lipid concentration ratios for sum PCBs, sum OCPs and sum PBDEs decreased significantly from 1.0+/-0.09 to 0.7+/-0.003, 1.1+/-0.1 to 0.7+/-0.02 and 1.2+/-0.14 to 0.8+/-0.05, respectively, during the course of egg laying. The profiles of the females and eggs differed significantly for the PCBs, OCPs and PBDEs. There was a higher contribution of lower chlorinated PCB congeners (CB 28, CB 52, CB 95, CB 101 and CB 110), BDE 183, p,p'-DDT and other less persistent OCPs in the females compared to their eggs. Maternal transfer in blue tits seemed to be selective for the more bioaccumulative and persistent congeners/compounds.     

Tissue-specific accumulation of polybrominated diphenyl ethers (PBDEs) including Deca-BDE and hexabromocyclododecanes (HBCDs) in harbor seals from the northwest Atlantic

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) are widely used flame retardants that enter coastal waters from multiple sources and biomagnify in marine food webs. PBDEs have been detected at relatively high concentrations in harbor seals, apex predators in the northwest Atlantic. Whereas tri- to hexa-BDEs readily biomagnified from prey fishes to seal blubber, Deca-BDE (BDE-209) did not biomagnify in blubber. To explore tissue-specific differences in the accumulation/biomagnification of BFRs, we analyzed tri- to Deca-BDES in liver of 56 harbor seals (6 adult males, 50 pups), and compared hepatic concentrations and biomagnification potential with those in blubber. HBCDs were analyzed in seal liver and blubber to enable similar comparisons. Hepatic ΣPBDE (tri- to Octa-BDE) concentrations (range 35–19,547 ng/g lipid weight, lw) were similar to blubber concentrations, while α-HBCD levels in seal liver (range 2–279 ng/g lw) were significantly higher than levels in blubber. Tissue distribution of PBDEs and α-HBCD varied significantly by age and, surprisingly, by gender among the pups. Biomagnification of α-HBCD from fish to seal liver and blubber was negligible to low, implying that harbor seals can metabolize this persistent isomer. Similar to the patterns in blubber, tri- through hexa-BDEs were highly biomagnified from fish to seal liver. In contrast, BDE-209 concentrations in liver were up to five times higher than those in blubber, which is consistent with observations that BDE-209 migrates to perfused tissues such as the liver in biota. Although detection frequency was low, BDE-209 levels in seal liver were up to ten times higher than those in their prey fish, suggesting that the accumulation/biomagnification of Deca-BDE in marine food webs is tissue-specific. As BDE-209 is the dominant PBDE found in marine sediments, its biomagnification in marine ecosystems is of concern.     

Polybrominated diphenyl ethers and polychlorinated biphenyls in human breast adipose samples from Brazil

Twenty five human breast adipose tissue samples were collected in Porto Alegre, Brazil during 2004-2005 and analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). SigmaPBDE concentrations (sum of tri- to hepta-BDEs) ranged from 0.19 to 132 ng/g lipid with a median of 1.51 ng/g lipid. These concentrations are 3- to 100-times lower than those reported from other countries, with the exception of Japan, probably reflecting lower usage of PBDE-containing products or lower exposures to these chemicals. The predominant congener was BDE-47, followed by BDEs 99, 183, 153 and 100. One individual in the dataset had about 70-times higher PBDE concentrations than the rest of the participants. SigmaPCB (sum of PCBs 118, 138, 153, 180) ranged from 30 to 339 ng/g lipid, with a median of 51 ng/g lipid. No age dependency was found for PBDEs (r=-0.800-0.374, p>0.05) or PCB 180 (r=0.278, p>0.05). On the other hand, PCBs 118, 138 and 153 did show age dependency (r=0.410-0.458, p<0.05). This is the first study to report levels of PBDEs in human breast adipose from Brazil.